Distillation



' P 1944. M. H. ITTNER DISTILLATIQN Filed July 23 1940 #54752 4M0 mvze 01 13 INVENTOR Patented Sept. 12, 1944 Martin Hill Ittner, Jersey City, N.

.L, assignor to Colgate-Palmolive-Peet Company, Jersey City, N. J., a corporation of Delaware Application July 28, 1940, Serial No. 346,970 Claims. (01. 202-53) This invention is directed to a method and apparatus for distilling high boiling liquids and more particularly it relates to the distillation of fatty acids. 7

A considerable number of different methods involving a reat variety of apparatus have been.

employed in the distillation of high boiling liquids: Under the designation of high boiling liquids I include fatty acids, higher boiling petroleum fractions and many other materials which are, or

may be, purified by distillation. The very nature of these bodies necessitates the employment of rather high temperatures for their distillation, and many of them are sufl'lciently affected by high temperatures to suffer appreciable decomposition. There are three factors which militate against ideal results in the distillation of some high boiling liquids. These are the'high temperatures required for distillation, contact with atmospheric air at elevated temperatures, and the length of time required to complete the distillation. In the case of many substances the first two of these factors are removed or substantially lessened by the employment of diminished pressure, or steam distillation, and preferably a combination of the two. In the case of more sensitive bodies the employment of so-called high vacua, or very low absolute pressures, is very helpful as these depress very considerably the temperature of distillation and at the same time remove air to such a-degree that its harmful influence is greatly lessened. The simultaneous employment of steam at low absolute pressures is helpful in still further depressing the effective temperature of distillation, and in more completely excluding air with its harmful influence.

In most types of batch distillation the process This necessitates a gradual raising of the still temperature, and the higher boiling material along with the polymerization products and the residue suffer from a very protracted cooking at the highest temperature employed and any attempt to avoid excessive temperatures at the end of the run can result only in lessened yield by leaving some of the desirable portion behind in the residue.

One means of attempting to avoid some of the difllculties mentioned above is to employ the socalled flash distillation" method. By this procedure the crude material to be distilled is heated rapidly in pipe stills to a very high temperature, much above the temperature of the actual distillation, the-object being to store up in the material while still in liquid condition enough heat units above the temperature of distillation to supply the latent heat necessary to convert the liquid into vapor almost at once after relieving pressure on the heated material. Although the material by this method is heated for only a comparatively short time, the excessively high 'temis a'progressive one with the last portions of the product remaining in the still exposed to heat and harmful chemical influences, such as cracking and polymerization, resulting in volatile impurities and an accumulation of higher boiling and tarry matters in the residue. These latter during distillation are projected into the fast rising vapors and are entrained with them to a degree that requires unusually efficient means of separation to prevent them from finding their way into the, condensers where they contaminate the distillate.

An additional disadvantage is met with in batch distillation of mixtures of ingredients having appreciably different boiling points, as with petroleum products, and fatty acids, for the more volatile ingredients pass over faster at first and the higher boiling portions remain until the end.

A fully increasing the pressure perature that must be employed, often several hundred-degrees above the actual distilling temperature, is apt to be very harmful and generally results in more or less undesirable cracking, polymerization and tar formation.

An object of the present invention is to facilitate the distillation of high boiling materials while obtaining an improved distillate. Another object is to provide a means of continuous dis tillation that will give substantially complete separation of the desirable-volatile material from the less desirable substantially Another object is to obtain a plete separation of entrained substantially commaterial from the distilling vapors while operating at faster rates of distillation than heretofore possible while producing material of good quality without harmdifferential between the still and the vacuum apparatus. Another object is to avoid the excessively high temperatures necessary for reasonably satisfactory flash distillations. Another object of the process of the invention is to realize substantial heat economies and ease of operation which will work together to lower the cost of distillation. The apparatus of the invention is simple of construction and comparatively inexpensive.

The invention furnishes method and means of continuous distillation of high boiling materials at temperatures very much below their normal boiling points even to substantially complete distillation of the volatile products and removal of non-volatile material.

the residual material without the necessity of employing excessively high temperatures such as must be used in any method depending entirely on ordinary flash distillation.

A specially favorable feature of the invention is that the means which are helpful inprodueing aration of entrained material; and vice versa,

the method employed for entrainment separation exercises a strong effect in increasing the heat transfer necessary to promote volatilization of the distillable material; and when direct steam is employed in the process, it promotes both indirect heat transfer and entrainment separation. These are in contrast with known methods of distillation in which means of heating and flashing, and steam stripping, etc., all promote entrainment, and in which one of these means does not supplement all the others beneficially.

The invention provides simple efilcient means of heating the still feed quickly and safely to a temperature suiliciently above the temperature of volatilization to induce rapid distillation, but very considerably below the temperatures necessary for ordinary flash distillation depending for complete volatilization on heat stored in the crude, or on heat stored in the crude augmented by the heat in a large weight of highly superheated steam that is used additionally for direct heating. The invention furnishes controlled. means of supp yin indirect heat in required amount to complete the volatilization of the volatilematerial without the employment of unnecessarily high temperatures. It also supplies a novel efficient means of effectively and evenly contacting the distilling liquid with the source .of indirect heat. By means of the invention rapid rates of distillation may be employed, without contamination of the distillate, which heretofore have been impossible of attainment without serious contamination of the distillate.

Other objects and accomplishments of the process and apparatus will be disclosed as the description is unfolded, and especially by reference to the accompanying drawing.

' Fig. 1 is an assembled diagrammatic illustration of a still suitable for carrying out the invenabout one third the inner diameter of the still. Inner drum 9 should be vertical and parallel to the axis of the still and accurately placed in the still so as to leave substantially equal space around it and between it and the still wall. The upper'end ID of inner drum 9 should be rounded with a curvature approximating the curvature of the still dome II, and should be spaced about of its diameter from the top of the still. It is desirable that the upper part of drum 9 shall be blocked off from the lower part by vapor tight partition l2, preferably located about on the level at which the crude feed material is introduced into the still I through nozzles l3, connected with a manifold pipe not shown, and sup plied by pipe ll throughcontrol valve IS. The

tion when supplied with proper condensers, not

shown, and vacuum equipment, not shown, and proper source of heat, not shown, and suitable auxiliaries, not shown.

Fig. 2 is a diagrammatic drawing partly in section of a preferred means of introducing feed to the still. I

Fig. 3 is an enlarged detailed drawing partly in section of one of the injection nozzles that may.

be employed to introduce feed to the still.

A more detailed description of the apparatus of Fig. 1 is as follows: A vertical still I is constructed in parts held together vacuum tight by flanges 2 and connected to gooseneck 3 by flange 4. The middle section of the still is provided with a heating jacket 5 connected to a source of heat, as diphenyl vapor supplied from a heating boiler not shown and controlled by valve 6, the condensed liquid from the heating vapor returning to the heating boiler from the jacket by pipe 'I.- The bottom section 8 of the still is provided with and tightly attached to a central hollow drum 9 having an outer diameter preferably lower part of still w'all l is supplied with nozzles l3a, which may be similar to nozzles I3, and which are connected to a manifold not shown and may be supplied with superheated steam by pipe l6 from a source not shown, in amounts controlled by valve II -or otherwise. Inner drum 9 may be supplied with hot vapor, as for instance diphenyl vapor, through valve l8 and any liquid condensed from the heating v'apor within drum 9 may be conducted backto the heating boiler through pipe l9. The still is supplied with a runoff so that residue may be removed at will or substantially continuously through valve 20 to drum 2|. Drum 2| is provided with pipe connections and valves 22 which permit withdrawing air from the drum or breaking vacuum if desired. Drum 2| is also provided with an indirectsource of heat, supplied through valve 23, in order to maintain the residue in a liquid condition. It is also supplied with a suitable runoff controlled byvalve 24 and provided with pump 25 which permits withdrawal of residue without breaking vacuum. When inner hollow drum 9 is furnished with vapor tight partition l2 the heat supplied through valve l9 is-available on the walls of drum 9 up to partition l2 but not above. The still may be provided with peep glasses 26 through which ment where it can be condensed to water by suitable means employing either direct or indirect cooling means. The vapors from the distillation may be condensed in surface condensers employ ing indirect heat transfer and the cooling medium may be the crude still feed which thus absorbs heat from the condensing vapors. If the indirect heat transfer be countercurrent in direction the still feed may thus be brought close to the still vapor temperature by employment of recovered heat, thus eflecting substantial economies. The distilling vapors may alternatively be condensed .by contacting them indirectly with boiling water, and by generation of steam which may be used elsewhere in-the process or for other purposes if desired. I flndthat it is desirable to condense the greater part of the distilling vapors at a comparatively high temperature, as for instance appreciably above C., in order that objectionably smelling impurities, which are commonly also quite volatile, may be permitted to pass onward thus leaving the greater part of the the beneficial swirling motion benecessary and drum 9.ex'oept perhaps to overcome radiation 4-- v heated steam enters the sw rl-producing steam, t 'e value of whichhas been alreadyrpointe ut.

I have called attention to some'of the shortcomings of ordinary flash distillation, especially to the' two most notorious of these, the common practice of greatly overheatingthe feed, and the promotion of tion thereof. However, with the aid of the present invention, flash distillation maybe greatly improved and carried out with a very minimum of injury to the distillate with substantially complete absence of entrainment impurities therein. 1 may, for example, while operating on crude fatty acids derived from hydrolysis of cocoanut oil, heat these indirectly, substantially free from in order not to interfere with effect of the superheated entrainment rather than preven assasaa pointed out thatmost of the. heat requisite for vapor as it leaves the still through gooseneck I, and to supply another portion of the heat neeessary to complete volatilization of the volatile matter through heating elements 5 and'l, and

it has also been shown that substantially all of the heat necessary for the separation of volatile matter may be supplied to the feed-while'taking advantage in the volatilization of the novel features of the invention, it should also be the volatilization may be supplied through heating elements 5 and 9 by employing the feed at a lower temperature; but it is undesirable to supply feed at any lower temperature than the temperature of the vapors within the still as'this dissolved or emulsified water, to a temperature of about 298. C, by passing them rapidly under of using some steam, as recommended, are so pressure through a pipe provided with a suitable means of supplying heat, as for example diphenyl vapor, and inject them thus heated under pressure through nozzles l3 into a hot still operating under low absolute pressure, as for example 6 mm. absolute pressure. Under such circumstances all, oii-subst antially all, of the cocoanut,fatty acids will volatilize almost instantly on release of the pressure and the vapors thus formed will also almost instantly be freed from any unvolatilized material and pass out 39 of gooseneck 3 to the condensers or distilling column in purecondition, while the unvolatilized material, following directions generally tangential to the course of the vapor, will come in contact with the wall of the still and thus be pennanently removed from the vapors as a contaminating material and will flnd its way rapidly to the bottom of the still where it may be removed through valve 20 to drum 2|. When operating the still, entirely on the flash principle it-will not to supply heatthrough jacket 5 losses,but in any event it is important to provide good heat insulation to the still and gooseneck and to any auxiliary part of the equipment where heat helpful to the process might be dissipated to the atmosphere or otherwise.

(It is desirable in flash distillation by the present invention to supply a small amount of superheated steam through nozzles I3a, it being unnecessary to superheat it to any higher temperature than "applied to the feed just before injection through nozzles IS. The amount of steam thus injected through nozzles 13a need not be over about 5% to 7% of the weight of the feed taken, though more or less may be employed, its principal use being to help maintain in the vapors within the still while it also adds some heat that goes to make up for some heat that may be lost to the process.

'wou1d lessen the efficiency of the still.

The process may be'operated with or without 4 the employment of steam, as thatwhich is injected through nozzles l3a, but the advantages great that it will be found advantageous to use it in most cases. steam at any lower temperature than that of the distilling vapor within the still as thiswould rob heat from the process where it is- 'most ,needed. It is advantageous, however, that the steam employed shall be superheated somewhat above the temperature of the distilling vapors within the still although it is entirely unnecesful degrees of superheat commonly employed the process of the invention it adds some heat where it has a salutary effect, and also has the effect of rendering volatile matter more volatile, thus lowering the effective temperature of volatilization, in addition to the novel and very helpful feature of promoting separation of unvolatilized matter without detracting from its other advantages.

While the process thus far described provides for the substantially complete volatilization and removal of the volatile matter, it may be found desirable in some instances to modify the process, as for example by leaving a portion of the volatile matter unvolatilized to be removed with the residue. This may be accomplished. by lessening the amount of heat supplied with a so given amount ofsfeed taken, or by increasing the amount of feed without lessening the heatsupplied. An advantage in operating'dn this way is that it provides a simple method of segregating the last fraction ,of volatile matter which is generally of lower quality than the maifi body of the distillate. In operating in this way the residue containing some unvolatilized volatile matter may be drawn off through valve 20 continuously and, while still hot, be sent direct to a secand still, not shown, preferably of the same type,

which may be smaller. It will be found desirable, however'," to put this residue in its passage to the second still through an indirect heat exchanger vwhere it may be reheated to a temperature above the temperature of the vaporwithin the second still. The vapor issuing from the second still may go to a separate condenser which may be connected to the same vacuum system as the first still or tea separate one, or in cases 7 0 where it is not desirable-to segregate portions of ferred method of operation is -to preheat the feed somew t above e p re of th second still operating in accordance with the the condensate the vapor of the second still may.

be commingled with the vapor of the first still beyond the goosenecks before entering the condensing system. It will be found that where a It isundesirable to inject sary that it be raised'to the extreme and harmportion of the distillate, will be very much superior in quality to the redistilled residues heretofore obtained which are ordinarily very inferior due to cracking and high tar entrainment.-

While I have described the invention as pertaining to the distillation of high boiling liquids and more particularly to the distillation of fatty acids, it is not to be inferred therefore that the invention is not advantageously applicable in its novel features to the distillation of lower boiling liquids or even to the distillation of liquids in general, the term high boiling" being used more in a relative than in an absolute sense. Where direct steam is used in connection with the invention, separation of the condensed distillate from the steam is facilitated where the distillate has an appreciably higher boiling point than water.

While I have endeavored to give in my disclosure deflnite apparatus, and methods that may be performed therein, so that anyone skilled in the art may find nothing lacking for carrying out the invention, I do not confine myself herein to the exact methods or to the exact means disclosed, as these may obviously be varied without departing from the broad, novel feature which constitute the invention. I have for example shown a vertical cylindrical still with a smaller,

cylindrical inner heating dome within, the free space between these being approximately 90% of the volume of the still. I have described the appurtenances and arrangements that will en-' able one to carry out the invention, but I may also operate very advantageously with a still of a generally globular shape with an inner bulbous heating dome leaving a substantially even space between the inner surface of the still shell and bulbous heating dome which may vary anywhere from appreciably under 90% to.even more than 95% of the space within the still, while taking advantage of the principles of the invention without departing therefrom. I may even construct a still and operate it successfully in accordance with the invention without employing an inner cylinder or inner bulb, by careful adjustment and proportioning of the various nozzles so as to produce an even swirl within the still with substantial avoidance of short circuits, countercurrents, or cross currents; but I prefer the employment of the inner heating cylinder or bulb as with its use I am not only enabled to add more heat in a part of the still where it is advantageous to do so, but I can be assured of substantially complete absence of harmful vapor currents, thus giving a positive removal of entrainedmatter. The actual space occupied by an inner dome or bulb may easily be less than 10% of the whole and the general efilciency of the apparatus and even the capacity of the still is increased by its employment. Furthermore, I have cited for example the use of diphenyl vapor as a source of heat for the jacket and inner heating dome but I may obviously use other means of heating as for example diphenyloxide vapor or a mixture of diphenyloxide and diphenyl vapor, or other heating vapors possessing the requisite physical properties. I may even apply heat in desired amounts to desired portions of'the apparatus by electrical induction heating, or by other electrical means, or by other means.

While a definite still has been illustrated and described it is to be understood that the process of the invention is not to be restricted to any one structure but that other structures within the scope of the discosures and claim may be employed.

Iclaim:

1. An apparatus suitable for the distillation of high boiling liquids comprising a still shell with a vapor outlet centrally placed at its top, a heat- I ing surface within said still and centrally placed therein 50 as to leave a substantially free, even space around it within the shell of said still, said free space occupying more than about 80% of the space within the shell of said still, means providing for indirectly heating at least a portion of the shell of said still, injection nozzles for injecting feed liquid to be distilled substantially horizontally within said free space at an angle at the point of injection of about 45 with the wall of said still above at least a portion of the indirectly heated still shell, means near the bottom of said still for injecting steam substantially horizontally in controlled amounts into said free space at an angle at the point of injection of about 45 with the wall of said still, means for condensing the vapors from said still and means for removing non-volatilized matter from said still.

2. In the distillation of high boiling liquid without substantial chemical change, the steps comprising heating said liquid as still feed under pressure to a temperature in excess of the distilling temperature employed within a still,- said temperature of heating being not higher than the boiling point of said liquid at the pressure under which it is heated, thus assuring the presence of volatile liquid in liquid condition in said still feed,

and injecting said heated liquid stll feed wth smultaneous reducton in pressure, into said still, with volatilization of at least a portion of said liquid, the general direction of said injecting being substantially horizontal inwardly at an angle substantially less than 90 and substantially more than 0 with the wall of said still, the vapors thus formed being forced in passage through and from the still to follow generally spiral path within a free space between two surfaces having substantially concentric, circular horizontal cross sections.

3. In the distillation of liquid without substantial chemical change, the process comprising preheating said liquid in liquid condition under pressure to a temperature above the temperature requisite for the volatilization of said liquid in a still at the pressure at which said volatilization occurs, injecting said preheated liquid inwardly chordwise into said still with substantial reduction of pressure and volatilization of a portion of said liquid with formation of vapors, substantially simultaneously freeing the vapors thus formed from unvolatilized matter, said volatili-' zation and substantial freeing of unvolatilized matter from said vapors being effected within a free space in said still between two surfaces having substantially concentric, circular horizontal cross sections, said substantial freeing of vapors from unvolatilized matter being effected by forc- :ing said vapors to follow substantially spiral paths in their upward passage through said free space.

4. In the distillation of high boilingliquid without substantial decomposition, the process which comprises the steps of preheating said liquid under pressure suflicient to prevent substantial vaporization thereof during said preheating, the temperature of said preheating being above the boiling point of said liquid under an absolute pressure of about 25 mm. mercury, injecting said preheated liquid into a still operating at absolute pressure under about 25 mm. mercury, the general direction of said injecting being substantially horizontal inwardly chordwise and at an angle of about 45' 'with the wall of the still, said injecting being into vapor space within said still between two surfaces having substantially concentric, circular horizontal cross sections, the vapors formed in said vapor space being thus substantially freed from unvolatilized matter by impingement thereof against said surfaces, conducting the vapors through a vapor outlet located substantially above the level of said injecting and then condensing the vapors.

5. A process as in claim 4 in which a portion of at least one of said surfaces defining the vapor space within the still supplies additional heat toously injecting it substantially horizontally into the vapor space of said still, said injection being at an angle with the wall of the still substantially less than 90 and substantially greater than said vapor space being largely between two surfaces having substantially concentric, circular, horizontal cross sections throughout the major portion of the height of said vapor space, at least one of said two surfaces being provided with indirect heating means for a portion of said surface situated beneath the level at which said feed is injected into said vapor space, a vapor outlet connected with the upper part of said vapor space, and means for condensing vapors from said still.

8. A still as in claim '7 provided with means for maintaining a vacuum within said vapor space and vapor outlet.

9. A distilling apparatus for distilling volatile liquids without substantial chemical change comprising a still, said still being provided with means for heating liquid feed to be distilled, means for maintaining sufllcient pressure on said liquid feed during said heating to keep the liquid feed in a liquid state, means for releasing pressure on' said heated liquid feed and simultaneously injecting it substantially horizontally into the vapor space of said still, said injection being inwardly at an angle with the wall of the still substantially less than degrees and substantially greater than zero degrees, means for injecting steam substantially horizontally into said vapor space at a level below the injection of the feed to said vapor space, the general horizontal direction of said steam after injection into said vapor space being substantially the same as the general horizontal direction of the said feed after injection into said vapor space, said vapor space being largely between two surfaces having substantially concentric, circular horizontal cross sections throughout the major portion of the height of said vapor space, at least one of said two surfaces being provided with indirect heating means for a portion of said surface situated beneath the level at which said feed is injected into said vapor space, a vapor outlet connected with the upper part of said vapor space, and

means for condensing vapors from said still.

10. The process of distilling volatile fatty matter which comprises heating said fatty matter under pressure to a temperature at which a portion of said fatty matter would become volatilized at a lower pressure, injecting said heated fatty matter through a wall of a still into the vapor space thereof with reduction of pressure and simultaneous volatilization of a portion of said fatty matter, the pressure within the vapor space of said still being maintained at a low absolute pressure, the direction of injecting said fatty matter into said still being inwardly chordwise I and generally horizontal for causing the unvolatilized portion of said fatty matter to impinge against the walls of said still at substantially acute angles, substantially freeing the vapors from the unvolatilized matter with the aid of vapor circulation induced by said inward chordwise injecting, supplying indirect heat to the unvolatilized fatty matter at and below the points of impingement, supplementing said vapor circulation with the inward chordwise injection of hot steam so directed into said vapor space as to contact the heated unvolatilized matter with the volatilization of at least a further portion of said volatil fatty matter.

MARTIN HILL I'I'I'NER. 

